3-aryl-tetronic acid derivatives, the production thereof and the use thereof as antiparasitic agents

ABSTRACT

The present invention relates to new 3-aryl-4-hydroxy-Δ 3  -dihydrofuranone derivatives of the formula (I) ##STR1## in which A and B together with the carbon atom to which they are bonded form an unsubstituted or substituted 5- to 7-membered ring which is interrupted by at least one hetero atom, 
     X represents alkyl, halogen or alkoxy, 
     Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl, 
     Z represents alkyl, halogen or alkoxy, 
     n represents a number 0, 1, 2 or 3, 
     G represents hydrogen (a) or one of the groups ##STR2## E represents a metal Ion equivalent or an ammonium ion, L represents oxygen or sulphur, 
     M represents oxygen or sulphur and 
     R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  have the meanings given in the description, to processes for their preparation, and to their use as pesticides.

This application is a 371 of PCT/EP95/04869 filed Dec. 11, 1995.

The present invention relates to new 3-aryl-4-hydroxy-Δ³-dihydro-furanone derivatives (3-aryl-tetronic acid derivatives), toprocesses for their preparation, and to their use as pesticides.

It has been disclosed that certain substituted Δ³ -dihydrofuran-2-onederivatives have herbicidal properties (cf. DE-A-4 014 420). Thesynthesis of the tetronic acid derivatives used as starting compounds(such as, for example,3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-Δ³ -dihydrofuran-2-one)is also described in DE-A-4 014 420. Compounds of a similar structureare known from the publication of Campbell et al., J. Chem. Soc., PerkinTrans. 1, 1985, (8) 1567-76, without an insecticidal and/or acaricidalactivity being mentioned. Furthermore, 3-aryl-Δ³ -dihydrofuranonederivatives having herbicidal, acaricidal and insecticidal propertiesare disclosed in EP-528 156, but the action described therein is notalways sufficient.

There have now been found new 3-aryl-4-hydroxy-Δ³ -dihydrofuranonederivatives of the formula (I) ##STR3## in which A and B together withthe carbon atom to which they are bonded form an unsubstituted orsubstituted 5- to 7-membered ring which is interrupted by at least onehetero atom,

X represents alkyl, halogen or alkoxy,

Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl,

Z represents alkyl, halogen or alkoxy,

n represents a number 0, 1, 2 or 3,

G represents hydrogen (a) or one of the groups ##STR4## E represents ametal ion equivalent or an ammonium ion, L represents oxygen or sulphur,

M represents oxygen or sulphur,

R¹ represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl,polyalkoxyalkyl, each of which is optionally substituted by halogen, orrepresents cycloalkyl which can be interrupted by at least one heteroatom and which is optionally substituted by halogen, alkyl or alkoxy, orrepresents in each case optionally substituted phenyl, phenylalkyl,hetaryl, phenoxyalkyl or hetaryloxyalkyl,

R² represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, each ofwhich is optionally substituted by halogen, or represents cycloalkylwhich is optionally substituted by halogen, alkoxy or alkyl, orrepresents in each case optionally substituted phenyl or benzyl,

R³, R⁴ and R⁵ independently of one another represent alkyl, alkoxy,alkylamino, dialkylamino, alkyltio, alkenylthio or cycloalkylthio, eachof which is optionally substituted by halogen, or represent in each caseoptionally substituted phenyl, benzyl, phenoxy or phenylthio, and

R⁶ and R⁷ independently of one another represent hydrogen, or representalkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl, each of which isoptionally substituted by halogen, or represent in each case optionallysubstituted phenyl or benzyl, or together represent an alkanediylradical which is optionally interrupted by oxygen or sulphur.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (Ia) to (Ig)result: ##STR5## in which

A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and n have theabovementioned meanings.

Due to one or more chiral centres, the compounds of the formulae (Ia) to(Ig) are generally obtained in the form of a stereoisomer mixture. Theycan be used in the form of their diastereomer mixtures, but also in theform of pure diastereomers or enantiomers.

Furthermore, it has been found that the new substituted 3-aryl-tetronicacid derivatives of the formula (I) are obtained by one of the processesdescribed hereinbelow.

(A) 3-Aryl-tetronic acids of the formula (Ia) ##STR6## in which A, B, X,Y, Z and n have the abovementioned meanings,

are obtained when carboxylic esters of the formula (II) ##STR7## inwhich A, B, X, Y, Z and n have the abovementioned meanings and

R⁸ represents alkyl, preferably C₁ -C₈ -alkyl,

are subjected to an intramolecular condensation reaction in the presenceof a diluent and in the presence of a base; and

(B) compounds of the formula (Ib) ##STR8## in which A, B, X, Y, Z, R¹and n have the abovementioned meanings,

are obtained when compounds of the formula (Ia) ##STR9## in which A, B,X, Y, Z and n have the abovementioned meanings, are reacted

α) with acid halides of the formula (III) ##STR10## in which R¹ has theabovementioned meanings and

Hal represents halogen, in particular chlorine and bromine,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent,

or

β) with carboxylic anhydrides of the formula (IV)

    R.sup.1 --CO--O--CO--R.sup.1                               (IV)

in which

R¹ has the abovementioned meanings,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent,

and

(C) compounds of the formula (Ic-1) ##STR11## in which A, B, X, Y, Z, R²and n have the abovementioned meanings and

M represents oxygen or sulphur,

are obtained when compounds of the formula (Ia) ##STR12## in which A, B,X, Y, Z and n have the abovementioned meanings,

are reacted with chloroformic esters or chloroformic thioesters of theformula (V)

    R.sup.2 --M--CO--Cl                                        (V)

in which

R² and M have the abovementioned meanings,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent;

and

(D) compounds of the formula (Ic-2) ##STR13## in which A, B, R², X, Y, Zand n have the abovementioned meanings and

M represents oxygen or sulphur

are obtained when compounds of the formula (Ia) ##STR14## in which A, B,X, Y, Z and n have the abovementioned meanings, are reacted

α) with chloromonothioformic esters or chlorodithioformic esters of theformula (VI) ##STR15## in which M and R² have the abovementionedmeanings,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent,

or

β) with carbon disulphide and then with alkyl halides of the formula(VII)

    R.sup.2 --Hal                                              (VII)

in which

R² has the abovementioned meanings and

Hal represents chlorine, bromine or iodine,

if appropriate in the presence of a diluent and if appropriate in thepresence of a base;

and

(E) compounds of the formula (Id) ##STR16## in which A, B, X, Y, Z, R³and n have the abovementioned meanings,

are obtained when compounds of the formula (Ia) ##STR17## in which A, B,X, Y, Z and n have the abovementioned meanings,

are reacted with sulphonyl chlorides of the formula (VIII)

    R.sup.3 --SO.sub.2 --Cl                                    (VIII)

in which

R³ has the abovementioned meanings,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent;

and

(F) compounds of the formula (Ie) ##STR18## in which A, B, L, X, Y, Z,R⁴, R⁵ and n have the abovementioned meanings,

are obtained when

compounds of the formula (Ia) ##STR19## in which A, B, X, Y, Z and nhave the abovementioned meanings,

are reacted with phosphorus compounds of the formula (IX) ##STR20## inwhich L, R⁴ and R⁵ have the abovementioned meanings and

Hal represents halogen, in particular chlorine and bromine,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent; and

(G) compounds of the formula (If) ##STR21## in which A, B, X, Y, Z and nhave the abovementioned meanings and

E represents a metal ion equivalent or an ammonium ion

are obtained when compounds of the formula (Ia) ##STR22## in which A, B,X, Y, Z and n have the abovementioned meanings,

are reacted with metal compounds or amines of the formulae (X) or (XI)##STR23## in which Me represents mono- or divalent metal ions, forexample alkali metal or alkaline earth metal ions, such as, for example,Li⁺, Na⁺, K⁺, Ca²⁺ or Mg²⁺,

t represents the number 1 or 2,

R¹⁰, R¹¹ and R¹² independently of one another represent hydrogen oralkyl (in particular C₁ -C₈ -alkyl) and

R¹³ represents hydrogen, hydroxyl or C₁ -C₄ -alkoxy,

if appropriate in the presence of a diluent.

(H) Furthermore, it has been found that compounds of the formula (I-g)##STR24## in which A, B, L, X, Y, Z, R⁶, R⁷ and n have theabovementioned meanings,

are obtained when compounds of the formula (Ia) ##STR25## in which A, B,X, Y, Z and n have the abovementioned meanings, are reacted

α) with compounds of the formula (XII)

    R.sup.6 --N═C═L                                    (XII)

in which

L and R⁶ have the abovementioned meanings,

if appropriate in the presence of a diluent and if appropriate in thepresence of a catalyst, or

β) with carbamoyl chlorides or thiocarbamoyl chlorides of the formula(XIII) ##STR26## in which L, R⁶ and R⁷ have the abovementioned meanings,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent.

Furthermore, it has been found that the new compounds of the formula (I)are distinguished by outstanding insecticidal and acaricidal actions.Preferred substituents or ranges of the radicals listed in the formulaementioned hereinabove and hereinbelow are illustrated in the followingtext.

A and B preferably represent C₄ -C₆ -alkanediyl which is optionallymonosubstituted or polysubstituted by identical or differentsubstituents from the series consisting of halogen, C₁ -C₈ -alkyl, C₃-C₈ -cycloalkyl, C₁ -C₈ -halogenoalkyl, C₁ -C₆ -alkoxy, C₁ -C₆-alkylthio or phenyl and in which one or two carbon atoms which are notdirectly adjacent are replaced by the group ##STR27## and/or oxygenand/or sulphur. A and B particularly preferably represent C₄ -C₅-alkanediyl which is optionally monosubstituted to tetrasubstituted byidentical or different substituents from the series consisting offluorine, chlorine, C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₁ -C₆-halogenoalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio or phenyl and in whichone or two carbon atoms which are not directly adjacent are replaced bythe group ##STR28## or by oxygen or by sulphur. A and B veryparticularly preferably represent C₄ -C₅ -alkanediyl which is optionallymonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl,trifluoromethyl, methoxy, methylthio or phenyl and in which one carbonatom is replaced by the group ##STR29## or by oxygen or by sulphur. Xpreferably represents C₁ -C₆ -alkyl, halogen or C₁ -C₆ -alkoxy.

X particularly preferably represents C₁ -C₄ -alkyl, fluorine, chlorine,bromine or C₁ -C₄ -alkoxy.

X very particularly preferably represents methyl, ethyl, n-propyl,iso-propyl, fluorine, chlorine, bromine, methoxy or ethoxy.

Y preferably represents hydrogen, C₁ -C₆ -alkyl, halogen, C₁ -C₆ -alkoxyor C₁ -C₃ -halogenoalkyl.

Y particularly preferably represents hydrogen, C₁ -C₄ -alkyl, fluorine,chlorine, bromine, C₁ -C₄ -alkoxy or C₁ -C₂ -halogenoalkyl.

Y very particularly preferably represents hydrogen, methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, fluorine, chlorine,bromine, methoxy, ethoxy or trifluoromethyl.

Z preferably represents C₁ -C₆ -alkyl, halogen or C₁ -C₆ -alkoxy.

Z particularly preferably represents C₁ -C₄ -alkyl, fluorine, chlorine,bromine or C₁ -C₄ -alkoxy.

Z very particularly preferably represents methyl, ethyl, propyl,i-propyl, n-butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine,methoxy or ethoxy.

G preferably represents hydrogen (a) or one of the groups ##STR30## inwhich E represents a metal ion equivalent or an ammonium ion,

L represents oxygen or sulphur and

M represents oxygen or sulphur.

R¹ preferably represents C₁ -C₂₀ -alkyl, C₂ -C₂₀ -alkenyl, C₁ -C₈-alkoxy-C₁ -C₈ -alkyl, C₁ -C₈ -alkylthio-C₁ -C₈ -alkyl or poly-C₁ -C₈-alkoxy-C₂ -C₈ -alkyl, each of which is optionally monosubstituted orpolysubstituted by halogen, or represents C₃ -C₈ -cycloalkyl which isoptionally substituted by halogen, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy andin which one or two methylene groups which are not directly adjacent areoptionally replaced by oxygen and/or sulphur,

or represents phenyl which is optionally monosubstituted topentasubstituted by halogen, nitro, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁-C₆ -halogenoalkyl, C₁ -C₆ -halogenoalkoxy, C₁ -C₆ -alkylthio or C₁ -C₆-alkylsulphonyl,

or represents phenyl-C₁ -C₆ -alkyl which is optionally monosubstitutedto pentasubstituted by halogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁ -C₆-halogenoalkyl or C₁ -C₆ -halogenoalkoxy,

or represents pyridyl, thienyl, furanyl, pyrazolyl, pyrimidyl orthiazolyl, each of which is optionally monosubstituted or disubstitutedby halogen or C₁ -C₆ -alkyl,

or represents phenoxy-C₁ -C₆ -alkyl which is optionally monosubstitutedto trisubstituted by halogen or C₁ -C₆ -alkyl,

or represents pyridinyloxy-C₁ -C₆ -alkyl, pyrimidinyloxy-C₁ -C₆ -alkylor thiazolyloxy-C₁ -C₆ -alkyl, each of which is optionallymonosubstituted or disubstituted by halogen, amino or C₁ -C₆ -alkyl.

R² preferably represents C₁ -C₂₀ -alkyl, C₂ -C₂₀ -alkenyl, C₁ -C₈-alkoxy-C₂ -C₈ -alkyl or poly-C₁ -C₈ -alkoxy-C₂ -C₈ -alkyl, each ofwhich is optionally monosubstituted or polysubstituted by halogen,

or represents C₃ -C₈ -cycloalkyl which is optionally monosubstituted orpolysubstituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

or represents phenyl or benzyl, each of which is optionallymonosubstituted to trisubstituted by halogen, nitro, C₁ -C₆ -alkyl, C₁-C₆ -alkoxy or C₁ -C₆ -halogenoalkyl.

R³ preferably represents C₁ -C₈ -alkyl which is optionallymonosubstituted or polysubstituted by halogen, or represents phenyl orbenzyl, each of which is optionally monosubstituted or polysubstitutedby halogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁ -C₄ -halogenoalkyl, C₁ -C₄-halogenoalkoxy, cyano or nitro.

R⁴ and R⁵ independently of one another preferably represent C₁ -C₈-alkyl, C₁ -C₈ -alkoxy, C₁ -C₈ -alkylamino, di-(C₁ -C₈)-alkylamino, C₁-C₈ -alkylthio, C₃ -C₆ -alkenylthio or C₃ -C₇ -cycloalkylthio, each ofwhich is optionally monosubstituted or polysubstituted by halogen,

or represent phenyl, phenoxy or phenylthio, each of which is optionallymonosubstituted or polysubstituted by halogen, nitro, cyano, C₁ -C₄-alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-halogenoalkylthio, C₁ -C₄ -alkyl or C₁ -C₄ -halogenoalkyl.

R⁶ and R⁷ independently of one another preferably represent hydrogen,

or represent C₁ -C₈ -alkyl, C₃ -C₈ -cycloalkyl, C₁ -C₈ -alkoxy, C₃ -C₈-alkenyl or C₁ -C₈ -alkoxy-C₁ -C₈ -alkyl, each of which is optionallymonosubstituted or polysubstituted by halogen,

or represent phenyl or benzyl, each of which is optionallymonosubstituted to trisubstituted by halogen, C₁ -C₈ -alkyl, C₁ -C₈-halogenoalkyl or C₁ -C₈ -alkoxy, or together represent a C₂ -C₆-alkanediyl radical which is optionally interrupted by oxygen orsulphur.

R⁹ preferably represents hydrogen, Q, COQ or CO₂ Q,

where

Q can assume the meanings which have been mentioned above as beingpreferred for R².

n preferably represents 0, 1 or 2.

G particularly preferably represents hydrogen (a) or one of the groups##STR31## in which E represents a metal ion equivalent or an ammoniumion,

L represents oxygen or sulphur and

M represents oxygen or sulphur.

R¹ particularly preferably represents C₁ -C₁₆ -alkyl, C₂ -C₁₆ -alkenyl,C₁ -C₆ -alkoxy-C₁ -C₆ -alkyl, C₁ -C₆ -alkylthio-C₁ -C₆ -alkyl or poly-C₁-C₆ -alkoxy-C₁ -C₆ -alkyl, each of which is optionally monosubstitutedto hexasubstituted by fluorine or chlorine,

or represents C₃ -C₇ -cycloalkyl which is optionally substituted byfluorine, chlorine, C₁ -C₅ -alkyl or C₁ -C₅ -alkoxy and in which one ortwo methylene groups which are not directly adjacent are optionallyreplaced by oxygen and/or sulphur,

or represents phenyl which is optionally monosubstituted totrisubstituted by fluorine, chlorine, bromine, nitro, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, C₁ -C₃ -halogenoalkyl, C₁ -C₃ -halogenoalkoxy, C₁ -C₄-alkylthio or C₁ -C₄ -alkylsulphonyl,

or represents phenyl-C₁ -C₄ -alkyl which is optionally monosubstitutedto trisubstituted by fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₃ -halogenoalkyl or C₁ -C₃ -halogenoalkoxy,

or represents pyridyl, thienyl, furanyl, pyrazolyl, pyrimidyl orthiazolyl, each of which is optionally monosubstituted or disubstitutedby fluorine, chlorine, bromine or C₁ -C₄ -alkyl,

or represents phenoxy-C₁ -C₅ -alkyl which is optionally monosubstitutedor disubstituted by fluorine, chlorine, bromine or C₁ -C₄ -alkyl,

or represents pyrimidinyloxy-C₁ -C₅ -alkyl, pyridinyloxy-C₁ -C₅ -alkylor thiazolyloxy-C₁ -C₅ -alkyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, aminoor C₁ -C₄ -alkyl.

R² particularly preferably represents C₁ -C₁₆ -alkyl, C₂ -C₁₆ -alkenyl,C₁ -C₆ -alkoxy-C₂ -C₆ -alkyl or poly-C₁ -C₆ -alkoxy-C₂ -C₆ -alkyl, eachof which is optionally monosubstituted to hexasubstituted by fluorine orchlorine,

or represents C₃ -C₇ -cycloalkyl which is optionally monosubstituted tohexasubstituted by fluorine, chlorine, C₁ -C₃ -alkyl or C₁ -C₃ -alkoxy,

or represents phenyl or benzyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, nitro,C₁ -C₄ -alkyl, C₁ -C₃ -alkoxy or C₁ -C₃ -halogenoalkyl.

R³ particularly preferably represents C₁ -C₆ -alkyl which is optionallymonosubstituted to hexasubstituted by fluorine or chlorine, orrepresents phenyl or benzyl, each of which is optionally monosubstitutedor disubstituted by fluorine, chlorine, bromine, C₁ -C₅ -alkyl, C₁ -C₅-alkoxy, C₁ -C₃ -halogenoalkyl, C₁ -C₃ -halogenoalkoxy, cyano or nitro.

R⁴ and R⁵ independently of one another particularly preferably representC₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁ -C₆ -alkylamino, di-(C₁-C₆)-alkylamino, C₁ -C₆ -alkylthio, C₃ -C₄ -alkenylthio or C₃ -C₆-cycloalkylthio, each of which is optionally monosubstituted tohexasubstituted by fluorine or chlorine,

or represent phenyl, phenoxy or phenylthio, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, nitro,cyano, C₁ -C₃ -alkoxy, C₁ -C₃ -halogenoalkoxy, C₁ -C₃ -alkylthio, C₁ -C₃-halogenoalkylthio, C₁ -C₃ -alkyl or C₁ -C₃ -halogenoalkyl.

R⁶ and R⁷ independently of one another particularly preferably representhydrogen, or represent C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₁ -C₆-alkoxy, C₃ -C₆ -alkenyl or C₁ -C₆ -alkoxy-C₁ -C₆ -alkyl, each of whichis optionally monosubstituted to hexasubstituted by fluorine orchlorine,

or represent phenyl or benzyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, C₁ -C₅-alkyl, C₁ -C₅ -halogenoalkyl or C₁ -C₅ -alkoxy, or together represent aC₂ -C₆ -alkanediyl radical which is optionally interrupted by oxygen orsulphur.

R⁹ particularly preferably represents hydrogen, Q, COQ or CO₂ Q,

where

Q represents C₁ -C₆ -alkyl, phenyl or benzyl.

n particularly preferably represents 0 or 1.

G very particularly preferably represents hydrogen (a) or one of thegroups ##STR32## in which E represents a metal ion equivalent or anammonium ion,

L represents oxygen or sulphur and

M represents oxygen or sulphur.

R¹ very particularly preferably represents C₁ -C₁₄ -alkyl, C₂ -C₁₄-alkenyl, C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl, C₁ -C₄ -alkylthio-C₁ -C₆ -alkylor poly-C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, each of which is optionallymonosubstituted to trisubstituted by fluorine or chlorine, or representsC₃ -C₆ -cycloalkyl which is optionally substituted by fluorine,chlorine, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl,methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, s-butoxy ort-butoxy and in which one methylene group is optionally replaced byoxygen or sulphur,

or represents phenyl which is optionally monosubstituted ordisubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl,i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,methylthio, ethylthio, methylsulphonyl, ethylsulphonyl or nitro,

or represents phenyl-C₁ -C₃ -alkyl which is optionally monosubstitutedor disubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl,i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,

or represents thienyl, furanyl or pyridyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, methylor ethyl,

or represents phenoxy-C₁ -C₄ -alkyl which is optionally monosubstitutedor disubstituted by fluorine, chlorine, methyl or ethyl,

or represents pyridyloxy-C₁ -C₄ -alkyl, pyrimidyloxy-C₁ -C₄ -alkyl orthiazolyloxy-C₁ -C₄ -alkyl, each of which is optionally monosubstitutedor disubstituted by fluorine, chlorine, amino, methyl or ethyl.

R² very particularly preferably represents C₁ -C₄ -alkyl, C₂ -C₁₄-alkenyl, C₁ -C₄ -alkoxy-C₂ -C₆ -alkyl or poly-C₁ -C₄ -alkoxy-C₂ -C₆-alkyl, each of which is optionally monosubstituted to trisubstituted byfluorine or chlorine,

or represents C₃ -C₆ -cycloalkyl which is optionally monosubstituted totrisubstituted by fluorine, chlorine, methyl, ethyl, propyl, iso-propylor methoxy,

or represents phenyl or benzyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, nitro, methyl,ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl.

R³ very particularly preferably represents methyl, ethyl, propyl orisopropyl, each of which is optionally monosubstituted to trisubstitutedby fluorine or chlorine, or represents phenyl or benzyl, each of whichis optionally monosubstituted or disubstituted by fluorine, chlorine,bromine, methyl, ethyl, propyl, iso-propyl, tert-butyl, methoxy, ethoxy,isopropoxy, tertbutoxy, trifluoromethyl, trifluoromethoxy, cyano ornitro.

R⁴ and R⁵ independently of one another very particularly preferablyrepresent C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylamino, di-(C₁-C₄)-alkylamino or C₁ -C₄ -alkylthio, each of which is optionallymonosubstituted to trisubstituted by fluorine or chlorine,

or represent phenyl, phenoxy or phenylthio, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, nitro,cyano, C₁ -C₂ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₂ -alkylthio, C₁ -C₂-fluoroalkylthio, C₁ -C₂ -alkyl or C₁ -C₂ -fluoroalkyl.

R⁶ and R⁷ independently of one another e particularly preferablyrepresent hydrogen,

or represent C₁ -C₄ -alkyl, C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkoxy, C₃ -C₄-alkenyl or C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, each of which is optionallymonosubstituted to trisubstituted by fluorine or chlorine,

or represent phenyl or benzyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, C₁ -C₄-alkyl, C₁ -C₄ -halogenoalkyl or C₁ -C₄ -alkoxy, or together represent aC₂ -C₆ -alkanediyl radical which is optionally interrupted by oxygen orsulphur.

R⁹ very particularly preferably represents hydrogen, Q, COQ or CO₂ Q,

where

Q represents C₁ -C₄ -alkyl, phenyl or benzyl.

n very particularly preferably represents 0 or 1.

In the definitions given, saturated or unsaturated hydrocarbon radicals,also in connection with hetero atoms such as, for example, alkoxy oralkylthio, can, wherever possible, be straight-chain or branched.

The optionally polysubstituted radicals can be substituted by theidentical or different substituents mentioned for these radicals.

The abovementioned definitions of radicals or illustrations, in generalor in preferred ranges, can be combined with each other as desired, thatis to say combinations between the respective ranges and preferredranges are also possible. They apply to the end products and,correspondingly, to the precursors and intermediates.

Preferred according to the invention are those compounds of the formula(I) in which there exists a combination of the meanings mentioned aboveas being preferred (preferable).

Particularly preferred according to the invention are those compounds ofthe formula (I) in which there exists a combination of the meaningsmentioned above as being particularly preferred.

Very particularly preferred according to the invention are thosecompounds of the formula (I) in which there exists a combination of themeanings mentioned above as being very particularly preferred.

A preferred group of compounds are those compounds of the formula (I) inwhich n represents the number 1 and the substituent Z is in the6-position of the phenyl radical.

A further preferred group of compounds are those compounds of theformula (I) in which n represents the number 0 and Y simultaneously doesnot represent hydrogen.

Another preferred group of compounds are those compounds of the formula(I) in which n represents the number 1 and Y simultaneously representshydrogen.

In addition to the compounds mentioned in the Preparation Examples, thecompounds of the formula (Ia) listed in Tables 1 to 4 below may bementioned individually:

                  TABLE 1                                                         ______________________________________                                         ##STR33##                                                                    X              Y            Z                                                 ______________________________________                                        CH.sub.3       CH.sub.3     H                                                 Cl             Cl           H                                                 CH.sub.3       Cl           H                                                 Cl             CH.sub.3     H                                                 CH.sub.3       OCH.sub.3    H                                                 OCH.sub.3      CH.sub.3     H                                                 Cl             OCH.sub.3    H                                                 OCH.sub.3      Cl           H                                                 OCH.sub.3      OCH.sub.3    H                                                 Cl             H            Cl                                                Cl             H            F                                                 Cl             H            OCH.sub.3                                         CH.sub.3       H            CH.sub.3                                          CH.sub.3       H            OCH.sub.3                                         CH.sub.3       H            Cl                                                OCH.sub.3      H            OCH.sub.3                                         CH.sub.3       CH.sub.3     CH.sub.3                                          CH.sub.3       CH.sub.3     OCH.sub.3                                         CH.sub.3       OCH.sub.3    CH.sub.3                                          Cl             Cl           Cl                                                Cl             CF.sub.3     Cl                                                ______________________________________                                    

Table 2 contains the compounds of the formula ##STR34## in which X, Yand Z have the meanings given in Table 1.

Table 3 contains the compounds of the formula ##STR35## in which X, Yand Z have the meanings given in Table 1.

Table 4 contains the compounds of the formula ##STR36## in which X, Yand Z have the meanings given in Table 1.

If, in accordance with process (A), ethyl1-(2,4-dichlorophenylacetyloxy)-4-oxacyclohexane-carboxylate is used,the course of the process according to the invention can be representedby the following equation: ##STR37##

If, in accordance with process (B) (Variant α),3-(2,4,6-trimethylphenyl)-5,5-(ethyleneoxaethylene)-tetronic acid andpivaloyl chloride are used as starting substances, the course of theprocess according to the invention can be represented by the followingequation: ##STR38##

If, in accordance with process (B) (Variant β),3-(2,4,6-trimethylphenyl)-5,5-ethyleneoxamethylene-tetronic acid andacetic anhydride are used as starting compounds, the course of theprocess according to the invention can be represented by the followingequation: ##STR39##

If, in accordance with process (C),3-(2,4,6-trimethylphenyl)-5,5-ethylene-oxamethylene-tetronic acid andethoxyethyl chloroformate are used as starting compounds, the course ofthe process according to the invention can be represented by thefollowing equation: ##STR40##

If, in accordance with process (Dα),3-(2,4,6-trimethylphenyl)-5,5-ethylene-oxaethylene-tetronic acid andmethyl chloromonothioformate are used as starting materials, the courseof the reaction can be represented as follows: ##STR41##

If, in accordance with process (Dβ),3-(2,4,6-trimethylphenyl)-5,5-ethylenethio-ethylene-tetronic acid,carbon disulphide and methyl iodide are used as starting components, thecourse of the reaction can be represented as follows: ##STR42##

If, in accordance with process (E),3-(2,4,6-trimethylphenyl)-5,5-methyleneoxa-propylene-tetronic acid andmethanesulphonyl chloride are used as starting materials, the course ofthe reaction can be represented by the following equation: ##STR43##

If, in accordance with process (F),3-(2,4-dimethylphenyl)-5,5-ethylene-thioethylene-tetronic acid and2,2,2-trifluoroethyl chloromethanethio-phosphonate are used as startingmaterials, the course of the reaction can be represented by thefollowing equation: ##STR44##

If, in accordance with process (G),3-(2,4,6-trimethylphenyl)-5,5-ethylene-oxa-methylene-tetronic acid andNaOH are used as components, the course of the process according to theinvention can be represented by the following equation: ##STR45##

If, in accordance with process (Hα),3-(2,4,6-trimethylphenyl)-5,5-ethylene-oxaethylene-tetronic acid andethyl isocyanate are used as starting materials, the course of thereaction can be represented by the following equation: ##STR46##

If, in accordance with process (Hβ),3-(2,4,6-trimethylphenyl)-5,5-(ethylene-acetylamino-ethylene-tetronicacid and dimethylcarbamoyl chloride are used as starting materials, thecourse of the reaction can be represented by the following equation:##STR47##

The compounds of the formula (II) ##STR48## in which A, B, X, Y, Z, nand R⁸ have the abovementioned meanings,

which are required as starting substances in the above process (A) arenew.

The compounds of the formula (II) are obtained, for example, when

2-hydroxycarboxylic acid derivatives of the formula (XIV) ##STR49## inwhich R^(8') represents hydrogen (XIVa) or alkyl (preferably C₁ -C₈-alkyl) (XIVb) and A and B have the abovementioned meanings

are acylated with phenylacetyl halides of the formula (XV) ##STR50## inwhich X, Y, Z and n have the abovementioned meanings and

Hal represents chlorine or bromine,

(Chem. Reviews 52, 237-416 (1953)); and, in the event that R^(8')=hydrogen, the compounds formed, of the formula (IIa) ##STR51## in whichA, B, X, Y, Z and n have the abovementioned meanings,

are, if appropriate, esterified (Chem. Ind. (London) 1568 (1968)).

Some of the compounds of the formula (XIV) are known and/or can beprepared by known processes, for example from the cyanohydrins of theformula (XVI) ##STR52## in which A and B have the abovementionedmeanings,

see, for example, Nasarow, Unkowskii, Zh. Obshch. Khim. 26, 3486 (1956)or Bennett, Waddington, J. Chem. Soc. 2831 (1929)!.

Some of the compounds of the formula (XVI) are known and/or can beprepared by known methods (for example Eichen, Fritz; Schmidt, Michal;Buchborn, Helga; Arch. Pharm. 320, 348-61, 1987; Sargsyan, M. S.;Ukrtumyan, S. A.; Gevorkyan A. A.; Arm. Khim. Zh 38 494-8, 1985).

The phenylacetyl halides of the formula (XV) are known and/or can beprepared by known methods see, for example, Lutz, Hinkley, J. Amer.Chem. Soc. 72, 4091 (1950), Harispe, Ann. Chim. (Paris) 11, 6, pp. 249,282, 283 (1936)!.

The acid halides of the formula (III), carboxylic anhydrides of theformula (IV), chloroformic esters or chloroformic thioesters of theformula (V), chloromonothioformic esters or chlorodithioformic esters ofthe formula (VI), alkyl halides of the formula (VII), sulphonylchlorides of the formula (VIII), phosphorus compounds of the formula(IX) and metal compounds or amines of the formulae (X) and (XI) andisocyanates of the formula (XII) or carbamoyl chlorides of the formula(XIII), all of which are furthermore required as starting substances forcarrying out processes (B), (C), (D), (E), (F), (G) and (H) according tothe invention, are generally known compounds of organic or inorganicchemistry.

Process (A) is characterized in that compounds of the formula (II) inwhich A, B, X, Y, Z, n and R⁸ have the abovementioned meanings aresubjected to an intramolecular condensation reaction in the presence ofbases.

Diluents which can be employed in process (A) according to the inventionare all inert organic solvents. The following can preferably be used:hydrocarbons, such as toluene and xylene, furthermore ethers, such asdibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether anddiglycol dimethyl ether, furthermore polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone, andalso alcohols, such as methanol, ethanol, propanol, isopropanol,butanol, iso-butanol and tert-butanol.

Bases (deprotonating agents) which can be used when carrying out process(A) according to the invention are all customary proton acceptors. Thefollowing can preferably be used: the oxides, hydroxides or carbonatesof alkali metals and alkaline earth metals, such as sodium hydroxide,potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate,potassium carbonate and calcium carbonate, all of which can also beemployed in the presence of phase transfer catalysts, such as, forexample, triethylbenzylammonium chloride, tetrabutylammonium bromide,®Adogen 464 (methyltrialkyl(C₈ -C₁₀)ammonium chloride) or TDA 1(tris-(methoxyethoxy-ethyl)-amine).

Alkali metals, such as sodium or potassium, can furthermore be used.Other substances which can be employed are the amides and hydrides ofalkali metals and alkaline earth metals, such as sodium amide, sodiumhydride and calcium hydride, and furthermore also alkali metalalcoholates, such as sodium methylate, sodium ethylate and potassiumtert-butylate.

When carrying out process (A) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between -30° C. and 250° C.,preferably between 0° C. and 150° C.

Process (A) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (A) according to the invention, the reactantof the formula (II) and the deprotonating base are generally employed inmolar amounts. However, it is also possible to use one or the othercomponent in a larger excess (up to 3 mol).

Process (Bα) is characterized in that compounds of the formula (Ia) arereacted with carboxylic acid halides of the formula (III).

Diluents which can be employed in process (Bα) according to theinvention are all solvents which are sufficiently inert to acid halides.The following can preferably be used: hydrocarbons, such as benzine,benzene, toluene, xylene and tetralin, furthermore halogenohydrocarbons,such as methylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, additionally ketones, such asacetone and methyl isopropyl ketone, moreover ethers, such as diethylether, tetrahydrofuran and dioxane, and also carboxylic esters, such asethyl acetate, or else strongly polar solvents, such as dimethylsulphoxide and sulpholane. If the acid halide is sufficiently stable tohydrolysis, the reaction can also be carried out in the presence ofwater.

Suitable acid-binding agents for the reaction in accordance with process(Bα) according to the invention are all customary acid acceptors. Thefollowing can preferably be used: tertiary amines, such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base andN,N-dimethylaniline, furthermore alkaline earth metal oxides, such asmagnesium oxide and calcium oxide, additionally alkali metal carbonatesand alkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate, and alkali metal hydroxides, such assodium hydroxide and potassium hydroxide.

When carrying out process (Bα) according to the invention, the reactiontemperatures can also be varied within a substantial range. In general,the process is carried out at temperatures between -20° C. and +150° C.,preferably between 0° C. and 100° C.

When carrying out process (Bα) according to the invention, the startingsubstances of the formula (Ia) and the carboxylic acid halide of theformula (III) are generally used in approximately equivalent amounts.However, it is also possible to employ the carboxylic acid halide in alarger excess (up to 5 mol). Working-up is carried out by customarymethods.

Process (Bβ) is characterized in that compounds of the formula (Ia) arereacted with carboxylic anhydrides of the formula (IV).

Diluents which can preferably be used for process (Bβ) according to theinvention are those which are also preferably suitable when acid halidesare used. Besides, an excess of carboxylic anhydride can also act as thediluent.

When carrying out process (Bβ) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between -20° C. and +150° C.,preferably between 0° C. and 100° C.

When carrying out process (Bβ) according to the invention, the startingsubstances of the formula (Ia) and the carboxylic anhydride of theformula (IV) are generally used in approximately equivalent amounts.However, it is also possible to employ the carboxylic anhydride in alarger excess (up to 5 mol). Working-up is carried out by customarymethods.

In general, a procedure is followed in which diluent and excesscarboxylic anhydride and also the carboxylic acid which forms areremoved by distillation or by washing with an organic solvent or withwater.

Process (C) is characterized in that compounds of the formula (Ia) arereacted with chloroformic esters or chloroformic thioesters of theformula (V).

Suitable acid-binding agents for the reaction in accordance with process(C) according to the invention are all customary acid acceptors. Thefollowing can preferably be used: tertiary amines, such astriethylamine, pyridine, DABCO, DBU, DBA, Hunig base andN,N-dimethylaniline, furthermore alkaline earth metal oxides, such asmagnesium oxide and calcium oxide, additionally alkali metal carbonatesand alkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate, and alkali metal hydroxides, such assodium hydroxide and potassium hydroxide.

Diluents which can be employed in process (C) according to the inventionare all solvents which are sufficiently inert to the compounds of theformula (V). The following can preferably be used: hydrocarbons, such asbenzine, benzene, toluene, xylene and tetralin, furthermorehalogenohydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, additionallyketones, such as acetone and methyl isopropyl ketone, moreover ethers,such as diethyl ether, tetrahydrofuran and dioxane, and also carboxylicesters, such as ethyl acetate, or else strongly polar solvents, such asdimethyl sulphoxide and sulpholane.

When carrying out process (C) according to the invention, the reactiontemperatures can be varied within a substantial range. If the process iscarried out in the presence of a diluent and of an acid-binding agent,the reaction temperatures are generally between -20° C. and +100° C.,preferably between 0° C. and 50° C.

Process (C) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (C) according to the invention, the startingsubstances of the formula (Ia) and the chloroformic ester, orchloroformic thioester, of the formula (V) are generally employed inapproximately equivalent amounts. However, it is also possible to employone or the other component in a larger excess (up to 2 mol). Working-upis carried out by customary methods. In general, a procedure is followedin which precipitated salts are removed and the remaining reactionmixture is concentrated by stripping off the diluent.

In preparation process (Dα), approximately 1 mol of chloromonothioformicester, or chlorodithioformic ester, of the formula (VI) is generallyreacted per mole of starting compound of the formula (Ia) at 0° to 120°C., preferably at 20° to 60° C.

Suitable diluents which are optionally added are all inert polar organicsolvents, such as ethers, carboxylic esters, halogenated hydrocarbons,amides, alcohols, sulphones or sulphoxides.

Substances which are preferably employed are methylene chloride, ethylacetate, tetrahydrofuran, dimethylformamide or dimethyl sulphoxide.

If, in a preferred embodiment, the enolate salt of the compound of theformula (Ia) is prepared by adding strong deprotonating agents, such as,for example, sodium hydride or potassium tertiary-butylate, a furtheraddition of acid-binding agents can be dispensed with.

If acid-binding agents are employed, then customary inorganic or organicbases are suitable, examples which may be mentioned being sodiumhydroxide, sodium carbonate, potassium carbonate, pyridine andtriethylamine.

The reaction can be carried out under atmospheric pressure or elevatedpressure, preferably under atmospheric pressure. Working-up is carriedout by customary methods.

In preparation process (Dβ), the equimolar amount, or an excess, ofcarbon disulphide is added per mole of starting compound of the formula(Ia). This process is preferably carried out at temperatures from 0° to50° C., in particular at 20° to 30° C.

Bases which can be employed in process (Dβ) are all customary protonacceptors. Substances which can preferably be used are alkali metalhydrides, alkali metal alcoholates, alkali metal carbonates, alkalimetal hydrogen carbonates, alkaline earth metal carbonates or alkalineearth metal hydrogen carbonates or nitrogen bases. Examples which may bementioned are sodium hydride, sodium methanolate, sodium hydroxide,calcium hydroxide, potassium carbonate, sodium hydrogen carbonate,triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline,diazabicyclooctane (DABCO), diazabicyclononene (DBN) anddiazabicycloundecene (DBU).

Diluents which can be used in this process are all customary solvents.

The following can preferably be used: aromatic hydrocarbons, such asbenzene or toluene, alcohols, such as methanol, ethanol, isopropanol orethylene glycol, nitriles, such as acetonitrile, ethers, such astetrahydrofuran or dioxane, amides, such as dimethylformamide, or otherpolar solvents, such as dimethyl sulphoxide or sulpholane.

Frequently, it appears expedient first to prepare the corresponding saltfrom the compound of the formula (Ia) by adding a deprotonating agent(such as, for example, potassium tertiary butylate or sodium hydride).The compound (Ia) is reacted with carbon disulphide until the formationof the intermediate compound is complete, for example after stirring atroom temperature for several hours.

The further reaction with the alkyl halide of the formula (VII) ispreferably carried out at 0° to 70° C., in particular at 20° to 50° C.At least the equimolar amount of alkyl halide is employed for thispurpose.

The process is carried out under atmospheric pressure or elevatedpressure, preferably under atmospheric pressure.

Again, working-up is carried out by customary methods.

In preparation process (E), approximately 1 mol of sulphonyl chloride(VIII) is reacted per mole of starting compound of the formula (Ia) at0° to 150° C., preferably at 20° to 70° C.

Suitable diluents which are optionally added are all inert polar organicsolvents, such as ethers, carboxylic esters, amides, nitriles,sulphones, sulphoxides or halogenated hydrocarbons, such as methylenechloride.

Substances which are preferably employed are ethyl acetate,tetrahydrofuran, dimethylformamide, dimethyl sulphoxide or methylenechloride.

If, in a preferred embodiment, the enolate salt of the compound of theformula (Ia) is synthesized by adding strong deprotonating agents (suchas, for example, sodium hydride or potassium tertiary butylate), thefurther addition of acid-binding agents can be dispensed with.

If acid-binding agents are employed, then customary inorganic or organicbases are suitable, examples which may be mentioned being sodiumhydroxide, sodium carbonate, potassium carbonate, triethylamine andpyridine.

The reaction can be carried out under atmospheric pressure or elevatedpressure, preferably under atmospheric pressure. Working-up is carriedout by customary methods.

In preparation process (F), 1 to 2 mol, preferably 1 to 1.3 mol, of thephosphorus compound of the formula (IX) to 1 mol of the compound (Ia)are reacted at temperatures between -40° C. and 150° C., preferablybetween -10° and 110° C., to obtain compounds of the structure (Ie).

Suitable diluents which are optionally added are all inert, polarorganic solvents, such as ethers, carboxylic esters, halogenatedhydrocarbons, amides, nitrites, sulphides, sulphones, sulphoxides andthe like.

Substances which are preferably employed are acetonitrile, ethylacetate, methylene chloride, tetrahydrofuran, dimethylformamide ordimethyl sulphoxide.

Suitable acid-binding agents which are optionally added are customaryinorganic or organic bases, such as hydroxides or carbonates. Exampleswhich may be mentioned are sodium hydroxide, sodium carbonate, potassiumcarbonate and pyrdine.

The reaction can be carried out under atmospheric pressure or underelevated pressure, preferably it is carried out under atmosphericpressure. Working-up is carried out by customary methods of organicchemistry. The end products obtained are preferably purified bycrystallization, chromatography or by so-called "incipientdistillation", i.e. removal of the volatile components in vacuo.

Process (G) is characterized in that compounds of the formula (Ia) arereacted with metal compounds of the formula (X) or amines of the formula(XI).

Diluents which can be employed for process (G) according to theinvention are preferably ethers, such as tetrahydrofuran or dioxane,diethyl ether, or else alcohols, such as methanol, ethanol orisopropanol, but also water. Process (G) according to the invention isgenerally carried out under atmospheric pressure. The reactiontemperatures are generally between -20° C. and 100° C., preferablybetween 0° C. and 50° C.

In preparation process (Hα), approximately 1 mol of isocyanate of theformula (XII) is reacted per mole of starting compound of the formula(Ia) at 0° to 100° C., preferably 20° to 50° C.

Suitable diluents which are optionally added are all inert organicsolvents, such as ethers, aromatic hydrocarbons, carboxylic esters,halogenated hydrocarbons, amides, nitriles, sulphones or sulphoxides.

If appropriate, catalysts may be added to accelerate the reaction.Catalysts which can be employed very advantageously are organotincompounds, such as, for example, dibutyltin dilaurate. The process ispreferably carried out under atmospheric pressure.

In preparation process (Hβ), approximately 1 mol of carbamoyl chlorideof the formula (XIII) is reacted per mole of starting compound of theformula (Ia) at 0° to 150° C., preferably 20° to 70° C.

Suitable diluents which are optionally added are all inert polar organicsolvents, such as ethers, carboxylic esters, halogenated hydrocarbons,amides, alcohols, sulphones or sulphoxides.

Substances which are preferably employed are dimethyl sulphoxide, ethylacetate, tetrahydrofuran, dimethylformamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compound of theformula (Ia) is synthesized by adding strong deprotonating agents (suchas, for example, sodium hydride or potassium tertiary butylate), thefurther addition of acid-binding agents can be dispensed with.

If acid-binding agents are employed, then customary inorganic or organicbases are suitable, examples which may be mentioned being sodiumhydroxide, sodium carbonate, potassium carbonate, triethylamine orpyridine.

The active compounds are suitable for combating animal pests, inparticular insects, arachnids and nematodes, encountered in agriculture,in forestry, in the protection of stored products and of materials, andin the hygiene field. They can preferably be employed as plantprotection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Pediculus humanus corporis,Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hayalopterus arundinis, Phylloxera vastarix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancadella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyla hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus miactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus sp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The compounds of the formula (I) according to the invention aredistinguished by a potent insecticidal and acaricidal activity. They arealso active against soil insects.

They can be employed particularly successfully against insects which areharmful to plants, such as, for example, against the larvae of themustard beetle (Phaedon cochleariae) and against the larvae of the greenrice leafhopper (Nephotettix cincticeps), or for combating mites whichare harmful to plants, such as, for example, against the two-spotted, orgreenhouse red, spider mite (Tetranychus urticae).

The active compounds of the formula (I) also have a certain herbicidalaction.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable:

for example ammonium salts and ground natural minerals, such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly disperse silica,alumina and silicates; as solid carriers for granules there aresuitable: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, as well as syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks;as emulsifying and/or foam-forming agents there are suitable: forexample non-ionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates aswell as albumen hydrolysis products; as dispersing agents there aresuitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colourants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas and substances produced by microorganisms,inter alia.

Examples of particularly advantageous components in the mixtures are thefollowing:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidin;2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl (E)-2-{2-6-(2-cyanophenoxy)pyrimidin-4-yloxy!-phenyl }-3-methoxyacrylate; methyl(E)-methoximino alpha-(o-tolyloxy)-o-tolyl!acetate; 2-phenylphenol(OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate, calciumpolysulphide, captafol, captan, carbendazim, carboxin, quinomethionate,chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,cymoxanil, cyproconazole, cyprofuram,

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine,drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,guazatine,

hexachlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole,iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb,mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb,methfuroxam, metiram, metsulfovax, myclobutanil, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin,polycarbamate, polyoxin, probenazole, prochloraz, procymidone,propamocarb, propiconazole, propineb, pyrazophos, pyrifenox,pyrimethanil, pyroquilon, quintozene (PCNB),

sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene,tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram,tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide,trichlamide, tricyclazole, tridemorph, triflumizole, triforine,triticonazole,

validamycin A, vinclozolin,

zineb, ziram.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furanecarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb,buprofezin, butocarboxin, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184 699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam,mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos,methidathion, methiocarb, methomyl, metolcarb, milbemectin,monocrotophos, moxidectin,

naled, NC 184, NI 25, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen, quinalphos,

RH 5992,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides:

for example anilides such as, for example, diflufenican and propanil;arylcarboxylic acids such as, for example, dichiloropicolinic acid,dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4-D,2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl,fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones such as, for example, chloridazon andnorflurazon; carbamates such as, for example, chlorpropham, desmedipham,phenmedipham and propham; chloroacetanilides such as, for example,alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlorand propachlor; dinitroanilines such as, for example, oryzalin,pendimethalin and trifluralin; diphenyl ethers such as, for example,acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen andoxyfluorfen; ureas such as, for example, chlortoluron, diuron,fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylaminessuch as, for example, alloxydim, clethodim, cycloxydim, sethoxydim andtralkoxydim; imidazolinones such as, for example, imazethapyr,imazamethabenz, imazapyr and imazaquin; nitriles such as, for example,bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example,mefenacet; sulfonylureas such as, for example, amidosulphuron,bensulphuron-methyl, chlorimuron-ethyl, chlorsulphuron, cinosulphuron,metsulphuron-methyl, nicosulphuron, primisulphuron,pyrazosulphuron-ethyl, thifensulphuron-methyl, triasulphuron andtribenuronmethyl; thiocarbamates such as, for example, butylate,cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb,thiobencarb and tri-allate; triazines such as, for example, atrazine,cyanazine, simazine, simetryn, terbutryn and terbutylazine; triazinonessuch as, for example, hexazinone, metamitron and metribuzin; others suchas, for example, aminotriazole, benfuresate, bentazone, cinmethylin,clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate,fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate,quinchlorac, quinmerac, sulphosate and tridiphane.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agents are compounds which increase the action ofthe active compounds, without it being necessary for the synergisticagent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms,

When used against hygiene and stored-product pests, the active compoundis distinguished by an excellent residual action on wood and clay aswell as a good stability to alkali on limed substrates.

The active compounds according to the invention are not only activeagainst plant, hygiene and stored-product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites)such as scaly ticks, Argasidae, scab mites, Trombidae, flies (stingingand sucking), parasitic fly larvae, lice, hair lice, bird lice andfleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenoptes spp.

From the order of the Mallophagida and the sub-orders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order Diptera and the sub-orders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica, Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp, Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp, Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

For example, they show an outstanding activity against Boophilusmicroplus, Lucilia cuprina and Musca domestica.

The active compounds of the formula (I) according to the invention arealso suitable for combating arthropods which attack agriculturallivestock, such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese,honeybees, other domestic animals such as, for example, dogs, cats, cagebirds, aquarium fish and so-called experimental animals, such as, forexample, hamsters, guinea pigs, rats and mice. By combating thesearthropods, it is intended to reduce deaths and reductions inperformance (in connection with meat, milk, wool, hides, eggs, honey andthe like), so that more economical and simpler animal management is madepossible by employing the active compounds according to the invention.

The active compounds according to the invention are used, in theveterinary sector, in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boli, the feed-through method, suppositories, by parenteraladministration, such as, for example, by means of injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal application, by dermal administration in theform of, for example, bathing or dipping, spraying, pouring on, spottingon, washing, dusting, and with the aid of active-compound-containingshaped articles, such as collars, ear tags, tail marks, limb bands,halters, marking devices and the like.

When used for livestock, poultry, domestic animals and the like, theactive compounds of the formula (I) can be used in the form offormulations (for example powders, emulsions, flowables) which comprise1 to 80% by weight of the active compounds, either directly or after100- to 10 000-fold dilution, or they can be used in the form of achemical bath.

Moreover, it has been found that the compounds of the formula (I)according to the invention have a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may preferably be mentioned by way of example, butnot by way of limitation:

Beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobiusmollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lytusplanicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale,Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apatemonachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylonspec., Dinoderus minutus.

Hymenopterans such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes formosanus.

Bristle tails, such as Lepisma saccharina.

Industrial materials are to be understood as meaning, in the presentcontext, nonliving materials such as, preferably, polymers, glues,sizes, paper and board, leather, wood and derived timber products, andpaints.

The material very particularly preferably to be protected against attackby insects is wood and derived timber products.

Wood and derived timber products which can be protected by thecomposition according to the invention, or by mixtures comprising thiscomposition, are to be understood as meaning, for example, structuraltimber, wooden beams, railway sleepers, bridge components, jetties,wooden vehicles, boxes, pallets, containers, telegraph poles, woodlaggings, windows and doors made of wood, plywood, chipboard, joinery ortimber products which are quite generally used in house building orbuilding joinery.

The active compounds can be used as such, in the form of concentrates orin the form of generally customary formulations, such as powders,granules, solutions, suspensions, emulsions or pastes.

The abovementioned formulations can be prepared in a manner known perse, for example by mixing the active compounds with at least one solventor diluent, emulsifier, dispersant and/or binder or fixative, waterrepellent, if appropriate desiccants and UV stabilizers, and ifappropriate colourants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for protecting woodand derived timber products comprise the active compound according tothe invention in a concentration of 0.0001 to 95% by weight, inparticular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thespecies and the occurrence of the insects and on the medium. The optimumamount to be employed can in each case be determined by series of testsupon use. However, it is generally sufficient to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound basedon the material to be protected.

The solvent and/or diluent used is an organic chemical solvent orsolvent mixture and/or an oily or oil-like organic chemical solvent orsolvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water and, if appropriate, anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably employed are oily oroil-like solvents with an evaporation number above 35 and a flash pointabove 30° C., preferably above 45° C. Such water-insoluble, oily andoil-like solvents of low volatility which are employed are suitablemineral oils or their aromatic fractions, or mineral-oil-comprisingsolvent mixtures, preferably white spirit, petroleum and/oralkylbenzene.

Substances which are advantageously used are mineral oils with a boilingrange of 170° to 220° C., white spirit with a boiling range of 170° to220° C., spindle oil with a boiling range of 250° to 350° C., petroleumor aromatics with a boiling range of 160° to 280° C., essence ofturpentine and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180° to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180° to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility and anevaporation number of above 35 and a flash point of above 30° C.,preferably above 45° C., can be replaced in part by organic chemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flash point ofabove 30° C., preferably of above 45° C., and that theinsecticide/fungicide mixture is soluble or emulsifiable in this solventmixture.

In a preferred embodiment, part of the organic chemical solvent orsolvent mixture is replaced by an aliphatic polar organic chemicalsolvent or solvent mixture. Substances which are preferably employed arealiphatic organic chemical solvents having hydroxyl and/or ester and/orether groups, such as, for example, glycol ethers, esters and the like.

Organic chemical binders which are used within the scope of the presentinvention are the synthetic resins and/or binding drying oils which canbe diluted with water and/or dissolved or dispersed or emulsified in theorganic chemical solvents employed and which are known per se, inparticular binders composed of, or containing, an acrylic resin, a vinylresin, for example polyvinyl acetate, polyester resin, polycondensationor polyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenol resin, hydrocarbon resin such as indene/coumarone resin,silicone resin, drying vegetable and/or drying oils and/or physicallydrying binders based on a natural and/or synthetic resin.

The synthetic resin used as binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances inamounts of up to 10% by weight may also be used as binders. In addition,colourants, pigments, water repellents, flavour improvers and inhibitorsor anticorrosives which are known per se and the like may be used.

According to the invention, the composition or concentrate preferablycomprises, as organic chemical binder, at least one alkyd resin ormodified alkyd resin and/or a drying vegetable oil. Substances which arepreferably used according to the invention are alkyd resins with an oilcontent of over 45% by weight, preferably 50 to 68% by weight.

Some or all of the abovementioned binder can be replaced by a fixative(mixture) or a plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers are from the chemical classes of the phthalic esters,such as dibutyl, dioctyl or benzylbutyl phthalate, phosphoric esterssuch as tributyl phosphate, adipic esters such as di-(2-ethylhexyl)adipate, stearates such as butyl stearate or amyl stearate, oleates suchas butyl oleate, glycerol ethers or higher-molecular-weight glycolethers, glycerol esters and p-toluenesulphonic esters.

Fixatives are chemically based on polyvinyl alkyl ethers, such as, forexample, polyvinyl methyl ether, or ketones, such as benzophenone andethylenebenzophenone.

Also particularly suitable as a solvent or diluent is water, ifappropriate in the form of a mixture with one or more of theabovementioned organic chemical solvents or diluents, emulsifiers anddispersants.

Particularly effective protection of wood is effected byindustrial-scale impregnating methods, for example vacuum, double-vacuumor pressure methods.

The ready-to-use compositions can, if appropriate, comprise otherinsecticides and, if appropriate, also one or more fungicides.

Suitable components which may additionally be admixed are preferably theinsecticides and fungicides listed in WO 94/29 268. The compoundsmentioned in this document are expressly a component of the presentapplication.

Components which can be very particularly preferably be admixed areinsecticides such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron,

and fungicides such as epoxyconazole, hexaconazole, azaconazole,propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,diclofluanid, tolylfluanid, 3-iodo-2-propinyl butylcarbamate,N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and use of the active compounds according to theinvention can be seen from the examples which follow.

PREPARATION EXAMPLES Example (Ia-1) ##STR53## 67.3 g (0.60 mol) ofpotassium tert-butylate are introduced into 400 ml of absolutedimethylformamide (DMF), a solution of 133.6 g (0.40 mol) of ethyl1-(2,4,6-tri-methylphenylacetyl-oxy)-4-oxa-cyclohexane-carboxylate isadded dropwise at 0° to 10° C., and the mixture is stirred overnight atroom temperature.

For working-up, the reaction mixture is slowly added dropwise to 2 l ofice-cooled 1N hydrochloric acid, the precipitate is filtered off withsuction and washed thoroughly with water, and the product is dried in avacuum drying oven.

For purification, the crude product is boiled with n-hexane, againfiltered off with suction and dried.

Yield: 91.6 g (79% of theory) of a solid, m.p.: 224°-226° C.

The following compounds of the formula (Ia) are obtained analogously orin accordance with the general preparation instructions:

(The following abbreviations are used in the tables:

Me=methyl, Et=ethyl, Pr=propyl, Bu=butyl, Ph=phenyl)

                                      TABLE 5                                     __________________________________________________________________________     ##STR54##                                                                    Ex.                              M.p.                                         No. A, B               X  Y  Z.sub.n                                                                           (°C.)                                 __________________________________________________________________________    Ia-2                                                                              CH.sub.2CH(CH.sub.3)O(CH.sub.2).sub.2                                                            Me Me 6-Me                                                                              235                                          Ia-3                                                                              CH.sub.2CH(CH.sub.3)O(CH.sub.2).sub.2                                                            Me Me H                                                Ia-4                                                                              CH.sub.2CH(CH.sub.3)O(CH.sub.2).sub.2                                                            Cl Cl H                                                Ia-5                                                                              CH.sub.2CH(CH.sub.3)O(CH.sub.2).sub.2                                                            Cl H  Cl                                               Ia-6                                                                              CH.sub.2CH(C.sub.2 H.sub.5)O(CH.sub.2).sub.2                                                     Me Me 6-Me                                                                              oil                                          Ia-7                                                                              CH.sub.2CH(C.sub.2 H.sub.5)O(CH.sub.2).sub.2                                                     Me Me H                                                Ia-8                                                                              CH.sub.2CH(C.sub.2 H.sub.5)O(CH.sub.2).sub.2                                                     Cl Cl H                                                Ia-9                                                                              CH.sub.2CH(C.sub.2 H.sub.5)O(CH.sub.2).sub.2                                                     Cl H  Cl                                               Ia-10                                                                             CH.sub.2C(CH.sub.3).sub.2O(CH.sub.2).sub.2                                                       Me Me 6-Me                                             Ia-11                                                                             CH.sub.2C(CH.sub.3).sub.2O(CH.sub.2).sub.2                                                       Me Me H                                                Ia-12                                                                             CH.sub.2C(CH.sub.3).sub.2O(CH.sub.2).sub.2                                                       Cl Cl H                                                Ia-13                                                                             CH.sub.2C(CH.sub.3).sub.2O(CH.sub.2).sub.2                                                       Cl H  6-Cl                                             Ia-14                                                                             CH.sub.2CH(Me)OCH(Me)CH.sub.2                                                                    Me Me 6-Me                                             Ia-15                                                                             CH.sub.2CH(Me)OCH(Me)CH.sub.2                                                                    Me Me H                                                Ia-16                                                                             CH.sub.2CH(Me)OCH(Me)CH.sub.2                                                                    Cl Cl H                                                Ia-17                                                                             CH.sub.2CH(Me)OCH(Me)CH.sub.2                                                                    Cl H  Cl                                               Ia-18                                                                             CH.sub.2O(CH.sub.2).sub.3                                                                        Me Me 6-Me                                             Ia-19                                                                             CH.sub.2OCH(Me)(CH.sub.2).sub.2                                                                  Me Me 6-Me                                             Ia-20                                                                             CH.sub.2O(CH.sub.2).sub.2                                                                        Me Me 6-Me                                             Ia-21                                                                             CH(Me)O(CH.sub.2).sub.2                                                                          Me Me 6-Me                                             Ia-22                                                                             CH.sub.2OCH(Me)CH.sub.2                                                                          Me Me 6-Me                                             Ia-23                                                                             CH.sub.2OCH.sub.2CH(Me)                                                                          Me Me 6-Me                                             Ia-24                                                                             (CH.sub.2).sub.2S(CH.sub.2).sub.2                                                                Me Me 6-Me                                                                              266-267                                      Ia-25                                                                             (CH.sub.2).sub.2S(CH.sub.2).sub.2                                                                Me Me H                                                Ia-26                                                                             (CH.sub.2).sub.2S(CH.sub.2).sub.2                                                                Cl Cl H                                                Ia-27                                                                             CH.sub.2CH(CH.sub.3)S(CH.sub.2).sub.2                                                            Me Me 6-Me                                             Ia-28                                                                             CH.sub.2CH(CH.sub.3)S(CH.sub.2).sub.2                                                            Me Me H                                                Ia-29                                                                             CH.sub.2CH(CH.sub.3)S(CH.sub.2).sub.2                                                            Cl Cl H                                                Ia-30                                                                             CH.sub.2S(CH.sub.2).sub.2                                                                        Me Me 6-Me                                                                              122-124                                      Ia-31                                                                             CH.sub.2S(CH.sub.2).sub.2                                                                        Me Me H                                                Ia-32                                                                             CH.sub.2S(CH.sub.2).sub.2                                                                        Cl Cl H                                                Ia-33                                                                             (CH.sub.2).sub.2N(COMe)(CH.sub.2).sub.2                                                          Me Me 6-Me                                                                              230                                          Ia-34                                                                             (CH.sub.2).sub.2N(COMe)(CH.sub.2).sub.2                                                          Me Me H                                                Ia-35                                                                             (CH.sub.2).sub.2N(COMe)(CH.sub.2).sub.2                                                          Cl Cl H                                                Ia-36                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me H  6-Me                                             Ia-37                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Cl Me H   219                                          Ia-38                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me Cl H                                                Ia-39                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Cl OMe                                                                              H                                                Ia-40                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me Ome                                                                              H                                                Ia-41                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me H  6-OMe                                            __________________________________________________________________________

Example (Ib-1) ##STR55## 28.8 g (0.10 mol) of3-(2,4,6-trimethylphenyl)-5,5-ethylene-oxa-ethylenetetronic acid ofExample (Ia-1) are introduced into 400 ml of absolute methylenechloride, 15.2 g (0.15 mol) of triethylamine are added, a solution of15.7 g (0.13 mol) of pivaloyl chloride is added dropwise at 0° to 10°C., and the mixture is stirred for a few hours at room temperature.

For working-up, the reaction mixture is washed in succession with 10%strength citric acid, sodium hydrogen carbonate solution and water, andthe organic phase is dried over sodium sulphate and evaporated.

For purification, the crude product is stirred with petroleum ether andfiltered off with suction.

Yield: 29.4 g (78% of theory) of a solid; m.p.: 119°-120° C.

The following compounds of the formulae (Ib) to (Ig) are obtainedanalogously or following the general preparation instructions:

                                      TABLE 6                                     __________________________________________________________________________     ##STR56##                                                                    Ex.                                       M.p.                                No.                                                                              A, B               X Y  Z.sub.n                                                                           R.sup.1    (°C.)                        __________________________________________________________________________    Ib-2                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              i-Pr       122                                 Ib-3                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe.sub.2CH.sub.2 Cl                                                                     170                                 Ib-4                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe.sub.2 -i-Pr                                                                          118                                 Ib-5                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CHCMe.sub.2                                                                              139                                 Ib-6                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              Ph         147-53                              Ib-7                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe.sub.2CH.sub.2 F                                                                      153-55                              Ib-8                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe(CH.sub.2 F).sub.2                                                                    158                                 Ib-9                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe(CH.sub.2 Cl).sub.2                                                                   188                                 Ib-10                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              C(CH.sub.2 Cl).sub.3                                                                     177                                 Ib-11                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe.sub.2CH.sub.2 OMe                                                                    177                                 Ib-12                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe(CH.sub.2 OMe).sub.2                                                                  104                                 Ib-13                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              C(CH.sub.2 OMe).sub.2                                                                    103                                 Ib-14                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe(CH.sub.2).sub.5                                                                      157                                 Ib-15                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe(CH.sub.2 OCH.sub.2 OCH.sub.2)                                                        176-79                              Ib-16                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              (CH.sub.2).sub.8CH.sub.3                                                                 oil                                 Ib-17                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              (CH.sub.2).sub.14CH.sub.3                                                                oil                                 Ib-18                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Cl                                                                              Cl H   Me                                             Ib-19                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me H   i-Pr                                           Ib-20                                                                            CH.sub.2CH(Me)O(CH.sub.2).sub.2                                                                  Me                                                                              Me 6-Me                                                                              i-Pr                                           Ib-21                                                                            CH.sub.2CH(Me)O(CH.sub.2).sub.2                                                                  Me                                                                              Me 6-Me                                                                              CH.sub.2 -t-Bu                                 Ib-22                                                                            CH.sub.2CH(Me)O(CH.sub.2).sub.2                                                                  Me                                                                              Me 6-Me                                                                              t-Bu       130                                 Ib-23                                                                            CH.sub.2CH(Me)O(CH.sub.2).sub.2                                                                  Me                                                                              Me 6-Me                                                                              CMe.sub.2CH.sub.2 Cl                           Ib-24                                                                            CH.sub.2CH(Me)OCH(Me)CH.sub.2                                                                    Me                                                                              Me 6-Me                                                                              t-Bu                                           Ib-25                                                                            CH.sub.2CH(Et)OCH(Me)CH.sub.2                                                                    Me                                                                              Me 6-Me                                                                              t-Bu                                           Ib-26                                                                            CH.sub.2C(CH.sub.3).sub.2O(CH.sub.2).sub.2                                                       Me                                                                              Me 6-Me                                                                              t-Bu                                           Ib-27                                                                            CH.sub.2O(CH.sub.2).sub.3                                                                        Me                                                                              Me 6-Me                                                                              t-Bu                                           Ib-28                                                                            CH.sub.2OCH(Me)(CH.sub.2).sub.2                                                                  Me                                                                              Me 6-Me                                                                              t-Bu                                           Ib-29                                                                            CH.sub.2O(CH.sub.2).sub.2                                                                        Me                                                                              Me 6-Me                                                                              t-Bu                                           Ib-30                                                                            (CH.sub.2).sub.2S(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              Me         198-200                             Ib-31                                                                            (CH.sub.2).sub.2S(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              t-Bu       113-115                             Ib-32                                                                            CH.sub.2S(CH.sub.2).sub.2                                                                        Me                                                                              Me 6-Me                                                                              Me         oil                                 Ib-33                                                                            CH.sub.2S(CH.sub.2).sub.2                                                                        Me                                                                              Me 6-Me                                                                              i-Pr       108-110                             Ib-34                                                                            CH.sub.2S(CH.sub.2).sub.2                                                                        Me                                                                              Me 6-Me                                                                              t-Bu       95-97                               Ib-35                                                                            (CH.sub.2).sub.2N(COMe)(CH.sub.2).sub.2                                                          Me                                                                              Me 6-Me                                                                              t-Bu        68                                 Ib-36                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CH.sub.2CFCF.sub.2                                                                       oil                                 Ib-37                                                                            (CH.sub.2).sub.2OCHEtCH.sub.2                                                                    Me                                                                              Me 6-Me                                                                              t-Bu       132                                 Ib-38                                                                            (CH.sub.2).sub.2OCHEtCH.sub.2                                                                    Me                                                                              Me 6-Me                                                                              CH.sub.2 -t-Bu                                                                            69                                 Ib-39                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              4-NO.sub.2Ph                                                                             191-195                             Ib-40                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              4-OMePh    112-116                             Ib-41                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe.sub.2 Et                                                                             130-132                             Ib-42                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me 6-Me                                                                              CMe.sub.2 CH.sub.2 OEt                                                                   126-129                             Ib-43                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              H  6-Me                                                                              t-Bu                                           Ib-44                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Cl                                                                              Me H   t-Bu       128                                 Ib-45                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Cl H   t-Bu                                           Ib-46                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Cl                                                                              OMe                                                                              H   t-Bu                                           Ib-47                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              OMe                                                                              H   t-Bu                                           Ib-48                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              H  6-OMe                                                                             t-Bu                                           __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________     ##STR57##                                                                    Ex.                                   M.p.                                    No.                                                                              A, B               X Y Z.sub.n                                                                          L M R.sup.2                                                                            (°C.)                            __________________________________________________________________________    Ic-1                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me                                                                              6-Me                                                                             O O i-Pr 104-05                                  Ic-2                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me                                                                              6-Me                                                                             O O t-Bu 107                                     Ic-3                                                                             CH.sub.2CH(Me)O(CH.sub.2).sub.2                                                                  Me                                                                              Me                                                                              6-Me                                                                             O O i-Pr oil                                     Ic-4                                                                             CH.sub.2CH(Me)OCH(Me)CH.sub.2                                                                    Me                                                                              Me                                                                              6-Me                                                                             O O s-Bu                                         Ic-5                                                                             CH.sub.2C(CH.sub.3).sub.2O(CH.sub.2).sub.2                                                       Me                                                                              Me                                                                              6-Me                                                                             O O i-Pr                                         lc-6                                                                             CH.sub.2S(CH.sub.2).sub.2                                                                        Me                                                                              Me                                                                              6-Me                                                                             O O i-Pr 119-121                                 Ic-7                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me                                                                              6-Me                                                                             O O CH.sub.2 t-Bu                                                                      145-147                                 Ic-8                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me                                                                              6-Me                                                                             O O i-Bu 96-98                                   Ic-9                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me                                                                              6-Me                                                                             O O s-Bu 111-113                                 Ic-10                                                                            (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                                Me                                                                              Me                                                                              6-Me                                                                             O S i-Pr 103-105                                 __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________     ##STR58##                                                                    Ex. No.                                                                           A     B     X  Y  Z   R.sup.3                                                                              M.p. °C.                              __________________________________________________________________________    Id-1                                                                              (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                         Me Me 6-Me                                                                              Me     171-173                                      Id-2                                                                              (CH.sub.2).sub.2O(CH.sub.2).sub.2                                                         Me Me 6-Me                                                                              4-MePh 171-173                                      __________________________________________________________________________

Example for the preparation of an intermediate of the formula (II):

Example (II-1) ##STR59## 31.3 g (0.18 mol) of ethyl1-hydroxy-4-oxa-cyclohexanecarboxylate are introduced into 150 ml ofmethylene chloride, 21.9 g (0.216 mol) of triethylamine are added, asolution of 38.9 g (0.20 mol) of mesitylacetyl chloride in 50 ml ofmethylene chloride is added dropwise at 0° to 10° C., and the mixture isstirred overnight at room temperature.

For working-up, the reaction mixture is washed in succession with 10%strength citric acid, sodium hydrogen carbonate solution and water, andthe organic phase is dried over magnesium sulphate and evaporated.

Yield: 60.6 g of an oil (quantitative).

The following compounds of the formula (II) are obtained analogously orin accordance with the general preparation instructions:

                                      TABLE 9                                     __________________________________________________________________________     ##STR60##                                                                    Ex.                                M.p.                                       No. A, B              X  Y  Z.sub.n                                                                           R.sup.8                                                                          (°C.)                               __________________________________________________________________________    II-2                                                                              CH.sub.2CH(Me)O(CH.sub.2).sub.2                                                                 Me Me 6-Me                                                                              Et oil                                        II-3                                                                              (CH.sub.2).sub.2S(CH.sub.2).sub.2                                                               Me Me 6-Me                                                                              Et oil                                        II-4                                                                              CH.sub.2S(CH.sub.2).sub.2                                                                       Me Me 6-Me                                                                              Et oil                                        II-5                                                                              (CH.sub.2).sub.2OCHMeCH.sub.2                                                                   Me Me 6-Me                                                                              Et oil                                        II-6                                                                              (CH.sub.2).sub.2OCHEtCH.sub.2                                                                   Me Me 6-Me                                                                              Et oil                                        II-7                                                                              (CH.sub.2).sub.2(NCOMe)(CH.sub.2).sub.2                                                         Me Me 6-Me                                                                              Et oil                                        __________________________________________________________________________

Example (XIV-1) ##STR61##

A mixture of 130 g (approximately 1 mol) of4-hydroxy-tetrahydropyran-4-carbonitrile and 1050 ml of dry ethanol issaturated with hydrochloric acid at -20° C. to 0° C. The mixture isallowed to come to room temperature, excess HCl is removed, the mixtureis concentrated in vacuo, 1.5 l of water are added, and the mixture isstirred for 3 hours at room temperature. It is filtered and extractedtwice using methylene chloride. After the solvent has been removed, 118g (61% of theory) of ethyl 4-hydroxy-tetrahydropyran-4-carboxylate ofb.p.₀.1 65° C. are obtained.

The following comparison compounds which are known from the prior artwere employed in the use examples: ##STR62## (all disclosed in EP-528156)

Example A

Myzus test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) which are severely infested with thepeach aphid (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the specified period of time, the destruction in % is determined.100% means that all the aphids have been killed; 0% means that none ofthe aphids have been killed.

In this test, a destruction of at least 95% was caused, after 6 days,for example, by the compounds of Preparation Examples Ia-1, Ib-1, Ib-12,Ib-15 and Ic-1 at an exemplary active compound concentration of 0.1%,while the prior-art compound (B) only caused a destruction of 70% at anactive compound concentration of 0.1%.

Example B

Critical concentration test/root-systemic action

Test insect: Aphis fabae

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

The preparation of active compound is intimately mixed with the soil.The concentration of the active compound in the preparation is ofpractically no importance here, only the amount by weight of activecompound per unit volume of soil, which is given in ppm (=mg/l), beingdecisive. The treated soil is transferred into pots and these areplanted with broad beans (Vicia faba). The active compound can in thisway be taken up from the soil by the roots of the plants and betransported into the leaves.

To demonstrate the root-systemic effect, the leaves are infested withthe abovementioned test animals after 8 days. After a further 6 days,the evaluation is made by counting or estimating the dead animals. Theroot-systemic action of the active compound is deduced from themortality figures. It is 100% if all the test animals have been killedand 0% if just as many test insects are still alive as in the case ofthe untreated control.

In this test, an activity of 100% was shown, for example, by thecompounds of Preparation Examples Ia-1, Ib-2, Ib-5, Ib-7, Ib-8, Ib-12,Ib-15, Ib-16, Ib-17 and Ic-2 at an exemplary active compoundconcentration of 200 ppm.

Example C

Nephotettix test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted withemulsifier-containing water to the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with larvae of the green rice leafhopper (Nephotettixcincticeps) while the seedlings are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the leafhoppers have been killed; 0% means that noneof the leafhoppers have been killed.

In this test, a destruction of 100% was shown, after 6 days, forexample, by the compounds of Preparation Examples Ia-1, Ib-1, Ib-16,Ic-1 and Ic-3 at an exemplary active compound concentration of 0.01%,while the known compound (A) caused no destruction.

Example D

Tetranychus test (OP resistant)

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) which are severely infested with alldevelopment stages of the two-spotted spider mite (Tetranychus urticae)are sprayed with a preparation of active compound of the desiredconcentration.

After the specified period of time, the destruction in % is determined.100% means that all the spider mites have been killed; 0% means thatnone of the spider mites have been killed.

In this test, for example, the compounds of Preparation Examples Ia-1,Ia-24, Ib-1, Ib-2, Ib-16, Ib-31 and Ic-1 showed a destruction of atleast 95% after 7 days at an exemplary active compound concentration of0.02% and the compounds of Preparation Examples Ib-5, Ib-7, Ib-11 andIb-22 showed a destruction of at least 98% after 7 days at an exemplaryactive compound concentration of 0.1%.

Example E

Panonychus test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted withemulsifier-containing water to the desired concentration.

Plum trees (Prunus domestica) approximately 30 cm in height which areseverely infested with all development stages of the fruit tree redspider mite (Panonychus ulmi) are sprayed with a preparation of activecompound of the desired concentration.

After the specified period of time, the destruction in % is determined.100% means that all the spider mites have been killed; 0% means thatnone of the spider mites have been killed.

In this test, for example, the compounds of Preparation Examples Ia-1,Ia-24, Ib-1, Ib-2, Ib-16, Ib-31 and Ic-1 caused a destruction of atleast 95% after 7 days at an exemplary active compound concentration of0.02%.

Example F

Fly larvae test/development-inhibitory action

Test animals: All larval stages of Lucilia cuprina (OP resistant) pupaeand adults (without contact with the active compound)!

Solvent: 35 parts by weight of ethylene glycol monomethyl ether 35 partsby weight of nonylphenol glycol ether

To prepare a suitable formulation, three parts by weight of activecompound are mixed with seven parts of the abovementionedsolvent/emulsifier mixture, and the resulting emulsion concentrate isdiluted with water to the concentration desired in each case.

For each concentration, 30 to 50 larvae are transferred to horsemeat (1cm³) in glass tubes, onto which 500 μl of the dilution to be tested arepipetted. The glass tubes are placed into plastic beakers whose bottomis covered with seasand and kept in a controlled-environment cabin (26°C.±1.5° C., relative humidity 70%±10%). The activity is checked after 24hours and 48 hours (larvicidal action). After the larvae have left(approximately 72 hours), the glass tubes are removed, and perforatedplastic lids pressed on to the beakers. After 1 1/2 times thedevelopment time (hatching of the control flies), the hatched flies andthe pupae/puparia are counted.

The criterion for the action is defined as the occurrence of death inthe treated larvae after 48 hours (larvicidal effect) or the inhibitionof adults hatching from the pupae or the inhibition of pupation. Thecriterion for in-vitro action of a substance is defined as theinhibition of fly development or a standstill of the development priorto the adult stage. 100% larvicidal action means that all the larvaehave died after 48 hours. 100% development-inhibitory action means thatno adult flies have hatched.

In this test, for example, the compounds of Preparation Examples Ia-2,Ia-24, Ib-4, Ib-15, Ib-22, Ib-24 and Ib-30 showed an action of in eachcase 100% at an exemplary active compound concentration of 1000 ppm.

We claim:
 1. A compound of the formula (I) ##STR63## in which A and Brepresent C₄ -C₆ -alkanediyl which is optionally monosubstituted orpolysubstituted by identical or different substituents selected from thegroup consisting of halogen, C₁ -C₈ -alkyl, C₃ -C₈ -cycloalkyl, C₁ -C₈-halogenoalkyl, C₁ -C₆ -alkoxy, C₁ -C₆ -alkylthio or phenyl and in whichone or two carbon atoms which are not directly adjacent are replaced bythe group ##STR64## or oxygen or sulphur, X represents C₁ -C₆ -alkyl,halogen or C₁ -C₆ -alkoxy,Y represents hydrogen, C₁ -C₆ -alkyl, halogen,C₁ -C₆ -alkoxy or C₁ -C₃ -halogenoalkyl, Z represents C₁ -C₆ -alkyl,halogen or C₁ -C₆ -alkoxy, G represents hydrogen (a) or one of thegroups ##STR65## in which E represents a metal ion equivalent or anammonium ion,L represents oxygen or sulphur and M represents oxygen orsulphur, R¹ represents C₁ -C₂₀ -alkyl, C₂ -C₂₀ -alkenyl, C₁ -C₈-alkoxy-C₁ -C₈ -alkyl, C₁ -C₈ -alkylthio-C₁ -C₈ -alkyl or poly-C₁ -C₈-alkoxy-C₂ -C₈ -alkyl, each of which is optionally monosubstituted orpolysubstituted by halogen, or represents C₃ -C₈ -cycloalkyl which isoptionally substituted by halogen, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy andin which one or two methylene groups which are not directly adjacent areoptionally replaced by oxygen or sulphur,or represents phenyl which isoptionally monosubstituted to pentasubstituted by halogen, nitro, C₁ -C₆-alkyl, C₁ -C₆ -alkoxy, C₁ -C₆ -halogenoalkyl, C₁ -C₆ -halogenoalkoxy,C₁ -C₆ -alkylthio or C₁ -C₆ -alkylsulphonyl, or represents phenyl-C₁ -C₆-alkyl which is optionally monosubstituted to pentasubstituted byhalogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁ -C₆ -halogenoalkyl or C₁ -C₆-halogenoalkoxy, or represents pyridyl, thienyl, furanyl, pyrazolyl,pyrimidyl or thiazolyl, each of which is optionally monosubstituted ordisubstituted by halogen or C₁ -C₆ -alkyl, or represents phenoxy-C₁ -C₆-alkyl which is optionally monosubstituted to trisubstituted by halogenor C₁ -C₆ -alkyl, or represents pyridinyloxy-C₁ -C₆ -alkyl,pyrimidinyloxy-C₁ -C₆ -alkyl or thiazolyloxy-C₁ -C₆ -alkyl, each ofwhich is optionally monosubstituted or disubstituted by halogen, aminoor C₁ -C₆ -alkyl, R² represents C₁ -C₂₀ -alkyl, C₂ -C₂₀ -alkenyl, C₁ -C₈-alkoxy-C₂ -C₈ -alkyl or poly-C₁ -C₈ -alkoxy-C₂ -C₈ -alkyl, each ofwhich is optionally monosubstituted or polysubstituted by halogen,orrepresents C₃ -C₈ -cycloalkyl which is optionally monosubstituted orpolysubstituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, orrepresents phenyl or benzyl, each of which is optionally monosubstitutedto trisubstituted by halogen, nitro, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy or C₁-C₆ -halogenoalkyl, R³ represents C₁ -C₈ -alkyl which is optionallymonosubstituted or polysubstituted by halogen, or represents phenyl orbenzyl, each of which is optionally monosubstituted or polysubstitutedby halogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁ -C₄ -halogenoalkyl, C₁ -C₄-halogenoalkoxy, cyano or nitro, R⁴ and R⁵ independently of one anotherrepresent C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, C₁ -C₈ -alkylamino, di-(C₁-C₈)-alkylamino, C₁ -C₈ -alkylthio, C₃ -C₆ -alkenylthio or C₃ -C₇-cycloalkylthio, each of which is optionally monosubstituted orpolysubstituted by halogen,or represent phenyl, phenoxy or phenylthio,each of which is optionally monosubstituted or polysubstituted byhalogen, nitro, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -halogenoalkylthio, C₁ -C₄ -alkyl or C₁ -C₄-halogenoalkyl, R⁶ and R⁷ independently of one another representhydrogen,or represent C₁ -C₈ -alkyl, C₃ -C₈ -cycloalkyl, C₁ -C₈ -alkoxy,C₃ -C₈ -alkenyl or C₁ -C₈ -alkoxy-C₁ -C₈ -alkyl, each of which isoptionally monosubstituted or polysubstituted by halogen, or representphenyl or benzyl, each of which is optionally monosubstituted totrisubstituted by halogen, C₁ -C₈ -alkyl, C₁ -C₈ -halogenoalkyl or C₁-C₈ -alkoxy, or together represent a C₂ -C₆ -alkanediyl radical which isoptionally interrupted by oxygen or sulphur, R⁹ represents hydrogen, Q,COQ or CO₂ Q, whereQ can assume the meanings which have been mentionedabove as being preferred for R² and n represents 0, 1 or
 2. 2. Compoundsof the formula (I) according to claim 1 in whichA and B represent C₄ -C₅-alkanediyl which is optionally monosubstituted to tetrasubstituted byidentical or different substituents from the series consisting offluorine, chlorine, C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₁ -C₆-halogenoalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkyl-thio or phenyl and inwhich one or two carbon atoms which are not directly adjacent arereplaced by the group ##STR66## or by oxygen or by sulphur, X representsC₁ -C₄ -alkyl, fluorine, chlorine, bromine or C₁ -C₄ -alkoxy, Yrepresents hydrogen, C₁ -C₆ -alkyl, fluorine, chlorine, bromine, C₁ -C₄-alkoxy or C₁ -C₂ -halogenoalkyl, Z represents C₁ -C₄ -alkyl, fluorine,chlorine, bromine or C₁ -C₄ -alkoxy, G represents hydrogen (a) or one ofthe groups ##STR67## in which E represents a metal ion equivalent or anammonium ion,L represents oxygen or sulphur and M represents oxygen orsulphur, R¹ represents C₁ -C₁₆ -alkyl, C₂ -C₁₆ -alkenyl, C₁ -C₆-alkoxy-C₁ -C₆ -alkyl, C₁ -C₆ -alkylthio-C₁ -C₆ -alkyl or poly-C₁ -C₆-alkoxy-C₁ -C₆ -alkyl, each of which is optionally monosubstituted tohexasubstituted by fluorine or chlorine,or represents C₃ -C₇ -cycloalkylwhich is optionally substituted by fluorine, chlorine, C₁ -C₅ -alkyl orC₁ -C₅ -alkoxy and in which one or two methylene groups which are notdirectly adjacent are optionally replaced by oxygen and/or sulphur, orrepresents phenyl which is optionally monosubstituted to trisubstitutedby fluorine, chlorine, bromine, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁-C₃ -halogenoalkyl, C₁ -C₃ -halogeno-alkoxy, C₁ -C₄ -alkylthio or C₁ -C₄-alkylsulphonyl, or represents phenyl-C₁ -C₄ -alkyl which is optionallymonosubstituted to trisubstituted by fluorine, chlorine, bromine, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₃ -halogenoalkyl or C₁ -C₃ -halogenoalkoxy,or represents pyridyl, thienyl, furanyl, pyrazolyl, pyrimidyl orthiazolyl, each of which is optionally monosubstituted or disubstitutedby fluorine, chlorine, bromine or C₁ -C₄ -alkyl, or representsphenoxy-C₁ -C₅ -alkyl which is optionally monosubstituted ordisubstituted by fluorine, chlorine, bromine or C₁ -C₄ -alkyl, orrepresents pyrimidinyloxy-C₁ -C₅ -alkyl, pyridinyloxy-C₁ -C₅ -alkyl orthiazolyloxy-C₁ -C₅ -alkyl, each of which is optionally monosubstitutedor disubstituted by fluorine, chlorine, bromine, amino or C₁ -C₄ -alkyl,R² represents C₁ -C₁₆ -alkyl, C₂ -C₁₆ -alkenyl, C₁ -C₆ -alkoxy-C₂ -C₆-alkyl or poly-C₁ -C₆ -alkoxy-C₂ -C₆ -alkyl, each of which is optionallymonosubstituted to hexasubstituted by fluorine or chlorine,or representsC₃ -C₇ -cycloalkyl which is optionally monosubstituted tohexasubstituted by fluorine, chlorine, C₁ -C₃ -alkyl or C₁ -C₃ -alkoxy,or represents phenyl or benzyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, nitro,C₁ -C₄ -alkyl, C₁ -C₃ -alkoxy or C₁ -C₃ -halogenoalkyl, R³ represents C₁-C₆ -alkyl which is optionally monosubstituted to hexasubstituted byfluorine or chlorine, or represents phenyl or benzyl, each of which isoptionally monosubstituted or disubstituted by fluorine, chlorine,bromine, C₁ -C₅ -alkyl, C₁ -C₅ -alkoxy, C₁ -C₃ -halogenoalkyl, C₁ -C₃-halogenoalkoxy, cyano or nitro, R⁴ and R⁵ independently of one anotherrepresent C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁ -C₆ -alkylamino, di-(C₁-C₆)-alkylamino, C₁ -C₆ -alkylthio, C₃ -C₄ -alkenylthio or C₃ -C₆-cycloalkylthio, each of which is optionally monosubstituted tohexasubstituted by fluorine or chlorine,or represent phenyl, phenoxy orphenylthio, each of which is optionally monosubstituted or disubstitutedby fluorine, chlorine, bromine, nitro, cyano, C₁ -C₃ -alkoxy, C₁ -C₃-halogenoalkoxy, C₁ -C₃ -alkylthio, C₁ -C₃ -halogenoalkylthio, C₁ -C₃-alkyl or C₁ -C₃ -halogenoalkyl, R⁶ and R⁷ independently of one anotherrepresent hydrogen, or represent C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₁-C₆ -alkoxy, C₃ -C₆ -alkenyl or C₁ -C₆ -alkoxy-C₁ -C₆ -alkyl, each ofwhich is optionally monosubstituted to hexasubstituted by fluorine orchlorine,or represent phenyl or benzyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, C₁ -C₅-alkyl, C₁ -C₅ -halogenoalkyl or C₁ -C₅ -alkoxy, or together represent aC₂ -C₆ -alkanediyl radical which is optionally interrupted by oxygen orsulphur, R⁹ represents hydrogen, Q, COQ or CO₂ Q, whereQ represents C₁-C₆ -alkyl, phenyl or benzyl and n represents 0 or
 1. 3. Compounds ofthe formula (I) according to claim 1, in whichA and B represent C₄ -C₅-alkanediyl which is optionally monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,sec-butyl, tert-butyl, cyclohexyl, trifluoromethyl, methoxy, methylthioor phenyl and in which one carbon atom is replaced by the group##STR68## X represents methyl, ethyl, n-propyl, iso-propyl, fluorine,chlorine, bromine, methoxy or ethoxy, Y represents hydrogen, methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, fluorine,chlorine, bromine, methoxy, ethoxy or trifluoromethyl, Z representsmethyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tert-butyl, fluorine,chlorine, bromine, methoxy or ethoxy, G represents hydrogen (a) or oneof the groups ##STR69## in which E represents a metal ion equivalent oran ammonium ion,L represents oxygen or sulphur and M represents oxygenor sulphur, R¹ represents C₁ -C₁₄ -alkyl, C₂ -C₁₄ -alkenyl, C₁ -C₄-alkoxy-C₁ -C₆ -alkyl, C₁ -C₄ -alkylthio-C₁ -C₆ -alkyl or poly-C₁ -C₄-alkoxy-C₁ -C₄ -alkyl, each of which is optionally monosubstituted totrisubstituted by fluorine or chlorine,or represents C₃ -C₆ -cycloalkylwhich is optionally substituted by fluorine, chlorine, methyl, ethyl,propyl, i-propyl, butyl, i-butyl, t-butyl, methoxy, ethoxy, propoxy,i-propoxy, butoxy, i-butoxy, s-butoxy or t-butoxy and in which onemethylene group is optionally replaced by oxygen or sulphur, orrepresents phenyl which is optionally monosubstituted or disubstitutedby fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl,methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio,ethylthio, methylsulphonyl, ethylsulphonyl or nitro, or representsphenyl-C₁ -C₃ -alkyl which is optionally monosubstituted ordisubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl,i-propyl, methoxy, ethoxy, tri-fluoromethyl or trifluoromethoxy, orrepresents thienyl, furanyl or pyridyl, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, methylor ethyl, or represents phenoxy-C₁ -C₄ -alkyl which is optionallymonosubstituted or disubstituted by fluorine, chlorine, methyl or ethyl,or represents pyridyloxy-C₁ -C₄ -alkyl, pyrimidyloxy-C₁ -C₄ -alkyl orthiazolyloxy-C₁ -C₄ -alkyl, each of which is optionally monosubstitutedor disubstituted by fluorine, chlorine, amino, methyl or ethyl, R²represents C₁ -C₁₄ -alkyl, C₂ -C₁₄ -alkenyl, C₁ -C₄ -alkoxy-C₁ -C₆-alkyl or poly-C₁ -C₄ -alkoxy-C₂ -C₆ -alkyl, each of which is optionallymonosubstituted to trisubstituted by fluorine or chlorine,or representsC₃ -C₆ -cycloalkyl which is optionally monosubstituted to trisubstitutedby fluorine, chlorine, methyl, ethyl, propyl, iso-propyl or methoxy, orrepresents phenyl or benzyl, each of which is optionally monosubstitutedor disubstituted by fluorine, chlorine, nitro, methyl, ethyl, propyl,1-propyl, methoxy, ethoxy or trifluoromethyl, R³ represents methyl,ethyl, propyl or isopropyl, each of which is optionally monosubstitutedto trisubstituted by fluorine or chlorine, or represents phenyl orbenzyl, each of which is optionally monosubstituted or disubstituted byfluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl,tert-butyl, methoxy, ethoxy, isopropoxy, tert-butoxy, trifluoromethyl,trifluoromethoxy, cyano or nitro, R⁴ and R⁵ independently of one anotherrepresent C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylamino, di-(C₁-C₄)-alkylamino or C₁ -C₄ -alkylthio, each of which is optionallymonosubstituted to trisubstituted by fluorine or chlorine,or representphenyl, phenoxy or phenylthio, each of which is optionallymonosubstituted or disubstituted by fluorine, chlorine, bromine, nitro,cyano, C₁ -C₂ -alkoxy, C₁ -C₂ -fluoro-alkoxy, C₁ -C₂ -alkylthio, C₁ -C₂-fluoroalkylthio, C₁ -C₂ -alkyl or C₁ -C₂ -fluoroalkyl, R⁶ and R⁷independently of one another represent hydrogen,or represent C₁ -C₄-alkyl, C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkoxy, C₃ -C₄ -alkenyl or C₁ -C₄-alkoxy-C₁ -C₄ -alkyl, each of which is optionally monosubstituted totrisubstituted by fluorine or chlorine, or represent phenyl or benzyl,each of which is optionally monosubstituted or disubstituted byfluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl or C₁-C₄ -alkoxy, or together represent a C₂ -C₆ -alkanediyl radical which isoptionally interrupted by oxygen or sulphur, R⁹ represents hydrogen, Q,COQ or CO₂ Q, whereQ represents C₁ -C₄ -alkyl, phenyl or benzyl and nrepresents 0 or
 1. 4. The compound of the formula (I) according to claim1 wherein one or two of the carbons in the C₄ -C₆ -alkanediyl group isreplaced by ##STR70##
 5. The compound of the formula (I) according toclaim 1 wherein A and B represent oxygen.
 6. The compound of the formula(I) according to claim 1 wherein A and B represent sulphur.
 7. Apesticidal composition comprising a pesticidally effective amount of acompound according to claim 1 and a diluent.
 8. A method of combatingunwanted pests which comprises administering to such pests or to a locusfrom which it is desired to exclude such pests a pesticidally effectiveamount of a compound according to claim 1.